Ligand-Enabled γ-C(sp3)-H Activation of Ketones

被引：121
|
作者：
Zhu, Ru-Yi [1 ]
Li, Zi-Qi [1 ]
Park, Han Seul [1 ]
Senanayake, Chris H. [2 ]
Yu, Jin-Quan [1 ]
机构：
[1] Scripps Res Inst, Dept Chem, 10550 N Torrey Pines Rd, La Jolla, CA 92037 USA
[2] Boehringer Ingelheim Pharmaceut Inc, Dept Chem Dev, 900 Ridgebury Rd, Ridgefield, CT 06877 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 10期
关键词：
C-H BONDS; CATALYZED INTRAMOLECULAR AMINATION; INTERMOLECULAR AMIDATION; C(SP(3))-H ARYLATION; PALLADIUM; FUNCTIONALIZATION; GAMMA;
D O I：
10.1021/jacs.8b01359
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
We report the first example of Pd(II)-catalyzed gamma-C(sp(3))-H activation of ketones directed by a practical 2,2-dimethyl aminooxyacetic acid auxiliary. 2-Pyridone ligands are identified to enable C(sp(3))-H activation for the first time. A rare six-membered palladacycle intermediate is isolated and characterized to elucidate the reaction mechanism. Both (hetero)arylation and vinylation of gamma-C(sp(3))-H bonds are demonstrated. Sequential beta- and gamma-C(sp(3))-H (hetero)arylation of muscone showcases the utility of this method for late-stage diversification. A convenient Mn(II)-catalyzed auxiliary removal is also developed to further underscore the practicality of this transformation.
引用
收藏
页码：3564 / 3568
页数：5
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